Impact Factor Value 3.
441
International Journal of Innovations in Engineering and Science, Vol. 2, No.7, 2017
www.ijies.net
Study of Electrical Conductivity of Lithium
Borate Ionically Conducting Glasses
M .D. Mehare
Assistant Professor
Priyadarshini Indira Gandhi College of Engineering, Nagpur, INDIA
Abstract Alkali ion conductors are of considerable
interest because of their possible applications in solid
state battery systems. The highly electropositive alkali
ion provides the possibility of large cell voltage and very
high energy densities. In general, particular material
will be required to act as either an electrode or an
electrolyte. Both application required high ionic
conductivity, preferably at ambient or relatively low
temperature. Lithium has a lower equivalent weight than
sodium or potassium. It is also more electropositive and
thus, provides the greater cell voltage than other two
ions. Lithium has additional advantage that it can be
handling more easily at room temperature than other
alkali metals. On the basis of theoretical background
and considering the advantage of amorphous solid
electrolyte it was thought imperative to develop a lithium
borate glass base solid electrolyte.
Keywords- Alkali ion conductors, solid state battery,
ionic conductivity, electropositive ion, amorphous solid
electrolyte, lithium borate glass base solid electrolyte.
INTRODUCTION
The recognition of fast lithium conduction in solids
dated from 1921, when Benrath and Deokopf [1]
discovered high temperature alpha phase of Li2SO4 until
the 1940.New emphasis has been given to this area in
1967 as a result of discovery of the higher Li +
conductivity in the alumina type layered structure. The
state of knowledge of Sodium lithium ion conductors up
to 1970 has been reviewed by Pizzine [2].About the
same time it become evident that lithium is potentially a
highly attractive element to use in kind of energy storage
system. Its light weight and high electro positivity as
well as relative ease with which it may be handled have
led to the proposal of many lower battery configurations
e-ISSN: 2456-3463
utilizing both liquid and solid electrolyte. During the
sane decades, glasses electrolyte with high ionic
conductivity have been found accidentally Kunze in
1973 [3].which where refer as super ionic conducting
glasses. The current interest in glassy solid electrolytes is
due to two main reasons.[a].Since they are X-ray
amorphous, there is wide scope for structural
investigation on microscopic level leading to theoretical
understanding of these of these materials.[b] Due to their
advantage [4] over their crystalline counter parts, they
have good prospects for being used in technological
applications. The ionic transport in amorphous solid
electrolyte has been reviewed by Souquet [5] in
1981.The fast ion conducting lithium glasses have been
reviewed by Kulkarni et al [6]. Progress in fast ions
glasses has been given by Minami[7] several glassy
electrolyte system has been discusses
I.1 Lithium Borate Glass Systems
These glasses are comprised of a network former B 2O3
in which the covalent bond structure ensured the rigidity
of the macromolecular structure and network modifier
(Li2O,Na2O,K2O,Ag2O,CaO,BaO etc) which introduce
ionic bond giving rise to cationic conduction. All oxygen
remain covalently bonded to cations of the forming
oxides in the elementary units. The micromolecular are
thus formed by the assembly of three units in which at
least one of the oxygen ions, called bridging ion is
shared with other non-bridging oxygen carrying
effective negative charge and therefore maintain in their
vicinity alkali or alkaline cations of the network modifier
oxide. These ionic bonds are generally assumed to be
randomly distributed over the macromolecular chain [5-
6].Otto [8] was the first to report glasses with high
lithium ion conductivity at relatively low temperature in
M2O:B2O3:SiO2 (M=Li,Na) system. He also suggested
that high lithium ion conductivity could be obtained in
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Impact Factor Value 3.441 e-ISSN: 2456-3463
International Journal of Innovations in Engineering and Science, Vol. 2, No.7, 2017
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borate glasses if more that 40 mole% lithium compounds represented by Deshpande et al and phenomenon called
could be incorporated in the glass without as mixed glass former effect ( MGFE ).
diversification. As a general rule, the conductivity of
oxide glasses increases with increasing amount of I.4.Glasses With Addition Of Salts:
network modifier such as Li2O,Na2O and K2O [9-11]. For increasing the ionic conductivity of glasses,different
approaches have been adopted .Of all the approaches,
I.2 Mixed Alkali Glass Systems: the addition of lithium salt viz. halides,sulphates,to
The NMR investigation for the borate glass added with lithium conducting glasses has been well established and
different alkali oxide modifier shows different structural widely studied one.In 1966 Otto [9] has reported that
variation for each oxide [8].In general the properties considerable amount of LiF,LiCl or Li2SO4 could be
exhibiting the mixed alkali effect typically reach either incorporated in lithium glasses without devitrifying
minimum or maximum depending upon the specific them.Shue and Tuller have examined the effect of CaO
property with substitution of second alkali e.g. electric addition to Li2O : LiCl : B2O3 glasses, since such
resistivity .This behavior for properties related to alkali addition have been believed to improve the durability in
ion movement found essentially independent of glass contact with lithiumCaO additions systematically
forming oxide being observed in silicate [12-16], borate decreases ionic conductivity in boroacite nad metaborate
[17-20],borosilicate [21],Phosphate [22-24] and glass systems,the lithium choride, which systematically
germinate [25-26] glasses. For mixed alkali glasses, the increases the conductivity,widens to calcium doping.The
large maximum in electrical resistivity has been reported glass in ternary system Li2O : (LiCl2):B2O3 (LCB) have
[27].Han et al [28] have studied the diffusion of Na + and been examine by Raman and NMR [ technique.The
Ag+ in binary Na2O:B2O3 glasses. The electrical enhancement of the lithium conduction in borate glasses
conductivity for 4-24 mole% of Na2O has been by addition of LiCl has also been observed by Muller et
measured from 373 oC to the temperature slightly below al .
Tg. Matusita et al [29] have measured the electrical
conductivity of [a] (1 X) Li2O :XbaO : 2SiO2 [b] (1 II EXPERIMENTAL TECHNIQUE
X) Li2O :XmgO : 2SiO2 [c] (1 X) Li2O :XcaO : 2SiO2
[d] (1 X) Li2O :XBaO : 2SiO2 in the temperature rang Material Preparation:
from room temperature to 725K. The mixed alkali effect For the glass preparation compositional parameter n
on the spectra of Ni2+ and Cu2+ on borate glasses has and y are defined to have systematic variation in
been reported by Ahmed et al[30]. former and modifier.
. 23+2
= =
2
I.3 Mixed Glass Former Systems:
2
It has been reported [31-32] that for the some molar = =
23 + 2
ration between lithium oxide glass former (B 2O5+
P2O5), the ionic conductivity, at room temperature
In the present work two different series are prepared
substantially higher in borophosphate glasses than in
with general composition 42.5Li2O (57.5-X) B2O3
pure borate or phosphate.Tatsumisago et al have studied
XSiO2. The series is specified with constancy of Li2O
the glass forming conductivity and thermal properties of
content given in table I and II
glasses containing high amount of Li2O in
Li2O: SiO2 : B2O3 , Li2O: B2O3 :P2O5, Li2O: P2O5 : SiO2 S. Glass Y Composition of mole% Specification
systems. According to them, the widest glass forming No No Li2O B2O3 SiO2
region has been observed in Li2O: SiO2: B2O3 system. 1 I1 0 42.5 57.5 0 For fixed
The composition dependence of conductivity has been n=1.35
2 I2 0.08695 42.5 52.5 5 y is varied
found to be closely related to Tg. The enhancement in
conductivity, mixing of two glass forming oxide, also 3 I3 0.1739 42.5 47.5 10
observed in Li2O: SiO2: B2O3 glasses containing large 4 I4 0.3478 42.5 37.5 20
amount of Li2O. Tsai and Greenblatt have investigated 5 I5 0.05217 42.5 27.5 30
the conductivity,IR and TMA for Li 2O: SiO2 : P2O5
system. These glasses have been prepared by Solgel
technique.The enhancement in the conductivity in
sulphide glasses (Li2O: SiO2 : GeS2) has been

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Impact Factor Value 3.441 e-ISSN: 2456-3463
International Journal of Innovations in Engineering and Science, Vol. 2, No.7, 2017
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S. Glass Y Composition of mole% Specification

No No Li2O B2O3 SiO2
1 I1 0 42.5 57.5 0
2 I2 0.08695 42.5 52.5 5
For fixed
3 I3 0.1739 42.5 47.5 10 n=1.35
4 I4 0.3478 42.5 37.5 20 y is varied
5 I5 0.05217 42.5 27.5 30

The initial ingredient were kept at kept at 100oC for 24

hours to remove the moisture and were weighted as per
molar ration with an accuracy of 0.00001 g using AE136
mettler (Switzerland) monopan electronic Balance. After
grinding them thoroughly in acetone for homogeneity,
then dried mixture kept furnace at 400oC for 2 hour, then
temperature increase to 600oC and maintain at 1 hour.
After evolution of decomposition product the melt was
kept at 900-1050 oC for 30 minute then viscous melt was
quenched in aluminum block kept at room temperature
.The quenching rate offered by the two blocks was found
to be approximately 102C/s .The prepared sample were
studied by electrical characterization.
Fig.2 Arrhenius plots for Li2O: B2O3: SiO2 mixed former
system (Series-II)
A detailed structure characteristic of entire LB series has
revealed the complete amorphousness of the
composition. The study of an temperature dependent
conductivity for this glasses, measured during heating
and cooling, so as to see the thermal hysteresis shown in
fig.3

III RESULTS AND DISCUSSION

I] AC Conductivity:

For the electrochemical device, bulk conductivity ( bulk)

is very important. bulk of each sample excluding
electrode effect, was determined from the real axis
intercept of the complex impedance analysis. It is also
excludes the contribution of displacement current.

Fig.3 The plot of log (T) Vs 103/T for 42.5 Li2O : 57.5
B2O3 : 0 SiO2

From the above result it is clear that the conductivity

does not follow the same path during heating and
cooling cycle, moreover they exhibit different slop
indicating attenuation in activation enthalpy.

II] CONCENTRATION DEPENDENT

CONDUCTIVITY:

The variation of conductivity as a function of Y for

series I and II are given in figure 4 and 5
Fig.1 Arrhenius plots for Li2O: B2O3: SiO2 mixed former
system (Series-I)
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Impact Factor Value 3.441
International Journal of Innovations in Engineering and Science, Vol. 2, No.7, 2017
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Fig4 Variation of conductivity as a function of Y for
series (I) at (250 oC)
Fig.5 Variation of conductivity as a function of Y for
series (II) at (250 oC)
It is seen from these curve that for each series,
characterize by a specific values of n , the sample with
y = 0.1 gives the maximum conductivity. For the y 0.2
the conductivity decreases.
IV CONCLUSION
The glasses prepared by quenching technique are found
to be ionic conductors. Amongst the entire sample
studied the glass with 42.5Li2O:57.5B2O3:0SiO2
composition exhibits maximum conductivity. Also, this
composition may find potential application as solid
electrolyte in electrochemical devices.
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e-ISSN: 2456-3463
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